Malodor Absorbent Polymer and Fiber

ABSTRACT

Thermoplastic polyolefin polymer composition, polymer chip, fiber, woven or nonwoven fabric, film, closures, laminates can comprise a polymer, a polymer and a nonvolatile polymer-compatible carboxylic acid. Thermoplastic polyolefin polymer composition can also comprise a polymer, a cyclodextrin-modified polymer and a nonvolatile polymer-compatible carboxylic acid. The carboxylic acid moiety of the polymer composition can react with basic materials in the polymer environment and reduce release of the basic material. The cyclodextrin can act to absorb or trap other contaminants or odors in the environment.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of application Ser. No.12/414,118, filed Mar. 30, 2009, which application is incorporatedherein by reference.

FIELD

The disclosure relates to thermoplastic polymer compositions, typicallypolyolefin compositions. The polyolefin materials can absorb a widerange of malodors in a variety of applications. The disclosure furtherrelates to polymer material, fiber, woven and nonwoven fabric, film,polymer webs of various thickness, rigid or semi rigid sheets, chips,barrier coatings and other useful polymer forms.

BACKGROUND

Synthetic fibers have found widespread use in a variety of applications.Synthetic fibers have been used to absorb fluids of various types and toneutralize malodors, for example from urine, wound exudate, blood andthe like. In some woven and nonwoven applications such as medical,diaper or feminine hygiene, there is a strong need to effectively absorbmalodors. Previously, traditional coated synthetic fibers have not beenable to satisfactorily absorb malodors at sufficient levels to be ofcommercial value.

There is a need to have a polymer composition and fiber that can bothabsorb fluid and neutralize or absorb typical malodorous materialincluding acidic, basic and both polar and non-polar nonionic malodors.

BRIEF DESCRIPTION

The thermoplastic polymer compositions comprise a blend of a polyolefinresin, a modified polyolefin resin and a non-volatile polymer compatiblecarboxylic acid. In one embodiment the modified polyolefin resin hascovalently bonded thereto structures that contain cyclodextrin (CD)moieties that are compatible with the thermoplastic polymer, wherein thecyclodextrin is free of an inclusion complex compound. The modifiedpolyolefin resin can have structures that contain carboxylic acidcompounds, dicarboxylic acid, anhydride compounds or an election of suchstructures that are compatible with the thermoplastic polymer.

Compositions of embodiments of the present invention have improvedmalodor neutralization properties. Unexpectedly, fibers and otherconstructs made from compositions of the present disclosure, having apolyolefin, a modified polyolefin and a non-volatile and polymercompatible carboxylic acid, have desired characteristics of neutralizinga large range of differing malodors and permeants. Unexpectedly, fibersand other constructs made from compositions of the present disclosure,having a polyolefin, a modified polyolefin, a covalently bondedcyclodextrin and a non-volatile and polymer compatible carboxylic acid,have desired characteristics of neutralizing a large range of differingmalodors and permeants. For example, not intended to be limiting, in afirst embodiment, the carboxylic acid moieties of the nonvolatilecarboxylic acid can neutralize basic malodor components e.g. ammonia,amines and the like. In a second embodiment, a polyolefin, a modifiedpolyolefin, a covalently bonded cyclodextrin and a non-volatile andpolymer compatible carboxylic acid can bind basically reacting malodorsand other permeants or inclusion compounds which otherwise would notreact, or react too slowly, with the carboxylic acid moieties (e.g.,aromatics, alcohols, halides and hydrogen halides, carboxylic acids andtheir esters, etc.). Thus, the combination of cyclodextrin and anon-volatile and polymer compatible carboxylic acid result in a fiber,or other construct, that is multipurpose with respect to neutralizationcharacteristics. All these characteristics have been achieved withoutdetriment to the processability (for example, extrudability) of thepolymer composition.

The term “modified polymer” as used in this specification means that apolymer such as a polyolefin has a either a covalently bonded linkinggroup capable to bond a cyclodextrin to a polymer or a cyclodextrincovalently bonded directly to the polymer or covalently bonded to thepolymer through a linking group.

The term “polyolefin compatible” or “polymer compatible” as used hereinmeans that a component, when added to or in contact with a compositioncontaining modified polyolefin or modified polymer as that term is usedin this specification, does not phase out of the composition and is notdetrimental to the pertinent physical characteristics of the resultingpolyolefin, such as tensile strength, melt index, color, odor or otherphysical characteristics the polyolefin or polymer would otherwise have.

The term “non-volatile” as used herein means a component added to apolyolefin that is not readily vaporized, suffers little loss onevaporation or has a low vapor pressure (e.g. less than 1.5 mm Hg), forexample, at polymer processing temperatures in the range of 100-260° C.

The term “neutralize” or “neutralization” as used herein means that achemical entity is changed, such that an undesirable characteristic(e.g. odor) is reduced, or eliminated. The change may be accomplished byabsorption, extreme pH, adsorption, chemisorption, chemical reaction orcombinations thereof.

The term “carboxylic acid” as used herein includes at least carboxylicacid, monocarboxylic acid, dicarboxylic acid and anhydrides.

The term “phase stable” refers to materials that are polyolefincompatible and remain in the stable mixture.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 are graphical representations of performance testingcomparison of the treated and control samples of nonwoven fabric productsamples. This testing involved paired comparison evaluation of bothsamples challenged with an ammonia/urine solution.

FIGS. 3A, 3B and 3C illustrate the dimensions of a cyclodextrin moleculewithout derivatization. The central pore comprises the hydrophilicspace, central pore or volume within the cyclodextrin molecule that canact as a site for absorbing a permeant or such contaminant. FIG. 3Arepresents α-cyclodextrin, FIG. 3B represents β-cyclodextrin and FIG. 3Crepresents γ-cyclodextrin. Such cyclodextrins have hydroxyl groupsformed on the perimeter of the molecule that can be available forreaction with, for example, anhydride groups or epoxide groups or bothon functionalized polyolefins.

DETAILED DESCRIPTION OF THE ILLUSTRATIVE EMBODIMENTS

Compositions, fibers and films prepared from compositions containing amodified polyolefin and a polyolefin with a non-volatile and polymercompatible carboxylic acid have unexpectedly been found to effectivelyneutralize malodors which arise from basic components, for example, butnot limited to ammonia and amines. In these systems the polymercompatible carboxylic acid can be melt-blended into the polyolefin andmodified polyolefin blend and is compatible with the polyolefin andmodified polyolefin blend.

Compositions, fibers and films prepared from compositions containing amodified polyolefin with a covalently bonded cyclodextrin and apolyolefin with a non-volatile and polymer compatible carboxylic acidhave unexpectedly been found to effectively neutralize malodors whicharise from basic components, for example, but not limited to ammonia andamines and nonionic polar and nonpolar malodors. In these systems thepolymer compatible carboxylic acid can be melt-blended into thepolyolefin and modified polyolefin blend and is compatible with thepolyolefin and modified polyolefin blend.

In one embodiment, the thermoplastic polymer compositions of theinvention comprise a blend of a polyolefin resin, a modified polyolefinresin and a non-volatile polymer compatible carboxylic acid. In a secondembodiment, the modified polyolefin resin contains from about 0.1 toabout 10 wt % or 1 to 9 wt % cyclodextrin. The thermoplastic polymercompositions comprise a blend of a major proportion of a polyolefinresin and between about 1 wt % to about 50 wt % of a modified polyolefinresin based on the polymer composition; and from about 0.1 wt % to about15 wt %, about 0.1 to 5 wt %, 0.2 wt % to about 3 wt % or 0.5 to 1.5 wt% a non-volatile and polymer compatible carboxylic acid based on thepolymer composition.

A cyclodextrin-modified polyolefin resin can be prepared by covalentlygrafting a cyclodextrin moiety onto a polyolefin or polyolefin blend tobe used in combination with a non-volatile and polymer compatiblecarboxylic acid. The grafting can be achieved by reacting a functionalgroup, such as a hydroxyl group, of cyclodextrin (CD) with a functionalgroup, such as an epoxy, acid, acid chloride or anhydride moiety, on thepolyolefin or polyolefin blend to form a bond between the cyclodextrinand the polyolefin. In another embodiment, an anhydride or epoxidecomponent of the functionalized polyolefin can be used to form areaction product. For example, a primary hydroxyl on the cyclodextrinreacts with a maleic anhydride moiety under conditions that convertsubstantially all anhydride groups to a half-ester. It has quiteunexpectedly been found that by such conversion it is possible tosignificantly change low molecular weight transport of organic compoundsin conventional polyolefin polymers using parent cyclodextrins.

Embodiments according to the present disclosure include a process for afunctionalized polyolefin and a polyolefin in a customary compoundingapparatus forming a compatible polyolefin composition that is combinedwith a non-volatile and polymer compatible carboxylic acid component.C₉-C₂₄ acids and polyacids are not typically compatible with PE or PPwithout a modified polymer. The modified olefin compatiblizes thenon-volatile carboxylic acid component, inhibiting the migration of thecarboxylic acid component to the surface of the article. Thisdifferentiates this application from that of fatty acids and soaps thatare used as mold release agents and lubricants where they are intendedto bleed to the surface because of their incompatibility.

Additionally, the vapor pressure characteristics of the non-volatile andpolymer compatible carboxylic acid can be tailored to the temperatureprofiles of the melt grafting process thus avoiding or minimizing thepresence of unsafe volatile components in the processing area.

The modified polyolefins and the Cyclodextrin grafted polymercompositions, according to the present disclosure, are useful inextruded or molded structures such as thin films, laminates, semi-rigidfilms and rigid containers as well as fibers. For instance, thesestructures provide functional properties for a sealant layer in flexiblefood packaging, a beverage contact layer for cartons and bottles,plastic closures and sealing element layers for bottle and jars forsauces, soups, puddings, baby food and wine, a non-contact layer inplastic fuel tanks, and polymers used to manufacture fiber, textile, andnonwoven compositions for disposable diapers.

Briefly, the disclosure comprises a polyolefin covalently bonded to a CDblended with a non-volatile and polymer compatible carboxylic acid. TheCD can be reacted with a functionalized polyolefin. Polyolefin can bemodified with a variety of known reactive functional groups can be usedto covalently bind CD. One version is modification or functionalizationof polyolefins where a peroxide initiator is used with variousunsaturated polar monomers to add chemically reactive moieties on thepolymer has important unexpected application when used in combinationwith a group of compounds in this present disclosure known ascyclodextrins and carboxylic acids.

In other embodiments, this disclosure relates to a polyolefin comprisinga polymer, a cyclodextrin-functionalized polyolefin and a non-volatileand polymer compatible carboxylic acid which act to neutralize malodors.

The disclosure further relates to a thermoplastic masterbatch comprisinga blend of a polyolefin and an anhydride-modified polyolefin resin and anon-volatile and polymer compatible carboxylic acid.

Embodiments in accordance with the present disclosure also include achip with a major dimension of less than about 10 mm. and a weight ofabout 20 to 50 mg, whereby the chip comprises compositions of thepresent disclosure as described above. Further embodiments include acontainer comprising an enclosed volume surrounded by a polyolefin web,the web comprised of compositions as described above, such containersbeing useful, for example, in the packaging of food. Additionally,fibers and films prepared from the compositions of the presentdisclosure are also included in accordance with the present disclosure.

Useful carboxylic acids for use in the compositions for malodorreduction include nonvolatile polymer compatible materials. Thematerials are used in the combined compositions and are not bonded tothe polyolefin. Such materials are high-molecular weighthydrocarbyl-substituted carboxylic acids or anhydrides. Thesehigh-molecular weight carboxylic acids are compatible with thecomposition containing the polymer and modified polymer and arenon-volatile and can act to absorb, adsorb or neutralize malodors. Lowmolecular weight carboxylic acids such as acetic acid, propionic acidand butyric acid have limited utility (i.e., vapor pressure and odor)compared with the high molecular weight carboxylic acids in disclosedherein. Typically these useful high molecular weight carboxylic acids oranhydrides or derivatives have hydrocarbyl groups or substituentscontaining an average of about 8 to about 500 carbon atoms, about 8 toabout 200 carbon atoms, about 9 to about 300 carbon atoms, about 10 toabout 50 carbon atoms and in some cases about 8 to about 40 carbonatoms.

The hydrocarbyl substituent can be derived from at least one moietyderived from the group of polymers such as ethylene, propylene,1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene,1-hexene, 1-heptene, 1-octene, styrene, 1-nonene, 1-decene, 1-undecene,1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene and 1-octadecene. The hydrocarbyl substituent can bederived from an alpha-olefin fractions such as those selected from thegroup consisting of C₁₅₋₂₅ alpha-olefins. Useful carboxylic acids can bemono- or polycarboxylic acids or anhydrides. The acid components can bealiphatic or aromatic. These components can contain polar substituentsprovided that the polar substituents are not present in portionssufficiently large to alter significantly the hydrocarbon character ofthe acid. Typical suitable polar substituents include halo, such aschloro and bromo, oxo, oxy, formyl, sulfenyl, sulfinyl, thio, nitro,etc. Such polar substituents, if present, preferably do not exceed about10% by weight of the total weight of the hydrocarbon portion of thesecomponents, exclusive of the carboxyl groups.

The monocarboxylic acids include aliphatic acids, isoaliphatic acids,i.e., acids having one or more lower acyclic pendant alkyl groups. Suchacids often contain a principle chain having at least about 14saturated, aliphatic carbon atoms. The chain can have 14 to 35 carbonatoms and at least one but usually no more than about four pendantacyclic alkyl groups. The principle chain of the acid is exemplified bygroups derived from tetradecane, pentadecane, hexadecane, heptadecane,octadecane, and eicosane. The pendant group can be a lower alkyl groupsuch as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,tert-butyl, n-hexyl, or other groups having up to about 7 carbon atoms.The pendant group can also be a polar-substituted alkyl group such aschloromethyl, bromobutyl, methoxyethyl, or the like, containing no morethan one polar substituent per group. Specific examples of suchisoaliphatic acids include 10-methyl-tetradecanoic acid,11-methyl-pentadecanoic acid, 3-ethyl-hexadecanoic acid,15-methyl-heptadecanoic acid, 16-methyl-heptadecanoic acid,6-methyl-octadecanoic acid, 8-methyl-octadecanoic acid,10-methyl-octadecanoic acid, 14-methyl-octadecanoic acid,16-methyloctadecanoic acid, 15-ethyl-heptadecanoic acid,3-chloromethyl-nonadecanoic acid, 7,8,9,10-tetramethyl-octadecanoicacid, and 2,9,10-trimethyl-octadecanoic acid.

The isoaliphatic acids include mixtures of branch-chain acids preparedby the isomerization of commercial fatty acids of, for example, about 16to about 20 carbon atoms. A useful method involves heating the fattyacid at a temperature above about 250° C. and a pressure between about200 and 700 psi, distilling the crude isomerized acid, and hydrogenatingthe distillate to produce a substantially saturated isomerized acid. Theisomerization can be promoted by a catalyst such as mineral clay,diatomaceous earth, aluminum chloride, zinc chloride, ferric chloride,or some other Friedel-Crafts catalyst. The concentration of the catalystmay be as low as about 0.01%, but more often from about 0.1% to about 3%by weight of the isomerization mixture. Water also promotes theisomerization and a small amount, from about 0.1% to about 5% by weight,of water may thus be advantageously added to the isomerization mixture.The unsaturated fatty acids from which the isoaliphatic acids may bederived include oleic acid, linoleic acid, linolenic acid, andcommercial fatty acid mixtures such as tall oil acids.

As disclosed in the foregoing patents, there are several processes forpreparing these high-molecular weight acids and anhydrides. Generally,these processes involve the reaction of (1) an ethylenically unsaturatedcarboxylic acid, acid halide, anhydride or ester reactant with (2) anethylenically unsaturated hydrocarbon or a chlorinated hydrocarbon at atemperature within the range of about 100°-300. degree. C. Thechlorinated hydrocarbon or ethylenically unsaturated hydrocarbonreactant can contain at least about 10 carbon atoms. In some embodimentsthe chlorinated hydrocarbon or ethylenically unsaturated hydrocarbonreactant can contain at least about 20 carbon atoms or more, at leastabout 30 carbon atoms or more, at least about 40 carbon atoms or more,or even at least about 50 carbon atoms. Additionally, the chlorinatedhydrocarbon or ethylenically unsaturated hydrocarbon reactant cancontain polar substituents, oil-solubilizing pendant groups, and can beunsaturated within the general limitations explained hereinabove.

When preparing the hydrocarbyl-substituted carboxylic acids, thecarboxylic acid reactant usually corresponds to the formulaR^(o)—(COOH)_(n), wherein R^(o) is characterized by the presence of atleast one ethylenically unsaturated carbon-to-carbon covalent bond and nis an integer from 1 to about 6 and preferably 1 or 2. The acidicreactant can also be the corresponding carboxylic acid halide,anhydride, ester, or other equivalent acylating agent and mixtures ofone or more of these. Ordinarily, the total number of carbon atoms inthe acidic reactant will not exceed about 20, preferably this numberwill not exceed about 10 and generally will not exceed about 6.Preferably the acidic reactant will have at least one ethylenic linkagein an alpha-, beta-position with respect to at least one carboxylfunction. Exemplary acidic reactants are acrylic acid, methacrylic acid,maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconicanhydride, citraconic acid, citraconic anhydride, mesaconic acid,glutaconic acid, chloromaleic acid, aconitic acid, crotonic acid,methylcrotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid, andthe like. Preferred acid reactants include acrylic acid, methacrylicacid, maleic acid, and maleic anhydride.

The ethylenically unsaturated hydrocarbon reactant and the chlorinatedhydrocarbon reactant used in the preparation of these high-molecularweight carboxylic acids and anhydrides can be high molecular weight,substantially saturated petroleum fractions and substantially saturatedolefin polymers and the corresponding chlorinated products. Polymers andchlorinated polymers derived from mono-olefins having from 2 to about 30carbon atoms, preferably 2 to about 20 carbon atoms, more preferably 2to about 12 carbon atoms, more preferably 2 to about 8 carbon atoms,more preferably 2 to about 6 carbon atoms are useful. Useful polymersare the polymers of 1-mono-olefins such as ethylene, propene, 1-butene,isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene,3-cyclohexyl-1-butene, and 2-methyl-5-propyl-1-hexene. Polymers ofmedial olefins, i.e., olefins in which the olefinic linkage is not atthe terminal position, likewise are useful. These are exemplified by2-butene, 3-pentene, 4-octene, 2-dodecene, etc.

Interpolymers of 1-mono-olefins such as illustrated above with eachother and with other interpolymerizable olefinic substances such asaromatic olefins, cyclic olefins, and polyolefins, are also usefulsources of the ethylenically unsaturated reactant. Such interpolymersinclude for example, those prepared by polymerizing isobutene withstyrene, isobutene with butadiene, propene with isoprene, propene withisobutene, ethylene with piperylene, isobutene with chloroprene,isobutene with p-methyl-styrene, 1-hexene with 1,3-hexadiene, 1-octenewith 1-hexene, 1-heptene with 1-pentene, 3-methyl-1-butene with1-octene, 3,3-dimethyl-1-pentene with 1-hexene, isobutene with styreneand piperylene, etc.

For reasons of hydrocarbon/polyolefin compatibility, the interpolymerscontemplated for use in preparing the high-molecular weight carboxylicacids and anhydrides useful in accordance with the present disclosurecan be substantially aliphatic and substantially saturated. That is,they should contain at least about 80% and preferably at least about95%, on a weight basis, of units derived from aliphatic mono-olefins.Preferably, they contain no more than about 5% olefinic bonds based onthe total number of the carbon-to-carbon covalent bonds present.

In one embodiment of the present disclosure, the polymers andchlorinated polymers are obtained by the polymerization of a C₄ refinerystream having a butene content of about 35% to about 75% by weight andan isobutene content of about 30% to about 60% by weight in the presenceof a Lewis acid catalyst such as aluminum chloride, chlorinated aluminaor boron trifluoride. These polyisobutenes can contain predominantlyisobutene repeat units of the configuration.

The chlorinated hydrocarbons and ethylenically unsaturated hydrocarbonsused in the preparation of the high-molecular weight carboxylic acidsand anhydrides can have up to about 500 carbon atoms per molecule.Preferred high-molecular weight carboxylic acids and anhydrides arethose containing hydrocarbyl groups of about 8 to 500 carbon atoms,about 9 to 300 carbon atoms and yet other embodiments about 10 to about50 carbon atoms. The high-molecular weight carboxylic acids andanhydrides may also be prepared by halogenating a high molecular weighthydrocarbon such as the above-described olefin polymers to produce apolyhalogenated product, converting the polyhalogenated product to apolynitrile, and then hydrolyzing the polynitrile. They may be preparedby oxidation of a high molecular weight polyhydric alcohol withpotassium permanganate, nitric acid, or a similar oxidizing agent.Another method involves the reaction of an olefin or a polar-substitutedhydrocarbon such as a chloropolyisobutene with an unsaturatedpolycarboxylic acid such as 2-pentene-1,3,5-tricarboxylic acid preparedby dehydration of citric acid.

The high-molecular weight carboxylic acid and anhydrides can also beobtained by reacting chlorinated carboxylic acids, anhydrides, acylhalides, and the like with ethylenically unsaturated hydrocarbons orethylenically unsaturated substituted hydrocarbons such as thepolyolefins and substituted polyolefins described hereinbefore in themanner described in U.S. Pat. No. 3,340,281, this patent beingincorporated herein by reference.

The low- and high-molecular weight carboxylic acid anhydrides can beobtained by dehydrating the corresponding diacids. Dehydration isreadily accomplished by heating the acid to a temperature above about70° C., preferably in the presence of a dehydration agent, e.g., aceticanhydride. Cyclic anhydrides are usually obtained from polycarboxylicacids having acid groups separated by no more than three carbon atomssuch as substituted succinic or glutaric acid, whereas linear anhydridesare usually obtained from polycarboxylic acids having the acid groupsseparated by four or more carbon atoms.

The low-molecular weight and high-molecular weight carboxylic acids usedherein include acid-producing derivatives thereof (in addition to theanhydrides) such as acyl halides and the like. Thus, the term“carboxylic acid” when used in the claims herein also refers to the acylhalides of such acids. These acyl halides can be prepared by thereaction of the carboxylic acids or their anhydrides with a halogenatingagent such as phosphorus tribromide, phosphorus pentachloride or thionylchloride using known techniques.

The addition of maleic anhydride to a normal alpha olefin generates analkenyl succinic anhydride. The “ene” reaction is an indirectsubstituting addition. It involves the reaction of an olefin with anallylic hydrogen (ene) with an enophile, e.g., maleic anhydride. Thereaction results in a new bond forming between two unsaturated carbonsand the allylic hydrogen transfers to the maleic anhydride through acyclic transition state. The reaction can be carried out using a rangeof normal alpha olefins from 1-butene to C₃₀₊ normal alpha olefin wax.The maleic anhydride molecule supplies the reactive anhydridefunctionality to the alkenyl succinic anhydride, while the long chainalkyl portion provides the hydrophobic properties.

Alkenyl succinic anhydride materials are available commercially such asmaleic anhydride derivatives comprises products with an alkenyl backbonethat starts at C₈ and progresses through to C₁₈. By changing the natureof the starting alkene (i.e. straight chain vs. isomerised form) thephysico-chemical properties of the resultant alkenyl succinic anhydride(e.g. solid vs. liquid form at room temperature) can be modified.Commercially available useful materials include: dodecenylsuccinicanhydride, n-tetradecenyl succinic anhydride, hexadecenylsuccinicanhydride, i-hexadecenyl succinic anhydride octadecenylsuccinicanhydride, and tetrapropenyl succinic anhydride. The polymethylenechains are shown in a specific conformation for convenience purposes anddo not conform to these structures in the composition of the invention.Hydrocarbyl-substituted succinic acids and anhydrides are preferredhigh-molecular weight carboxylic acids and anhydrides. These acids andanhydrides can be prepared by reacting maleic anhydride with an olefinor a chlorinated hydrocarbon such as a chlorinated polyolefin. Thereaction involves merely heating the two reactants at a temperature inthe range of about 100° C. to about 300° C., preferably, about 100 to200° C.

The product from this reaction is a hydrocarbyl-substituted succinicanhydride wherein the substituent is derived from the olefin orchlorinated hydrocarbon. The product may be hydrogenated to remove allor a portion of any ethylenically unsaturated covalent linkages bystandard hydrogenation procedures, if desired. Thehydrocarbyl-substituted succinic anhydrides may be hydrolyzed bytreatment with water or steam to the corresponding acid. Thehigh-molecular weight hydrocarbyl-substituted succinic acids andanhydrides can be represented by the formula:

wherein R is the hydrocarbyl substituent. Preferably R contains fromabout 10 to about 500 carbon atoms, more preferably from about 15 toabout 500 carbon atoms, or from about 18 to about 500 carbon atoms.

Cyclodextrin (CD) is a cyclic oligomer of α-D-glucopyranoside unitsformed by the action of certain enzymes such as cyclodextringlycotransferase (CGTase). Three cyclodextrins (alpha, beta, and gamma)are commercially available consisting of six, seven and eightα-1,4-linked glucose monomers, respectively (See FIGS. 1A, 1B and 1C).The most stable three-dimensional molecular configuration for theseoligosaccharides is a toroid with the smaller and larger opening of thetoroid presenting primary and secondary hydroxyl groups. The specificcoupling of the glucose monomers gives the CD a rigid, truncated conicalmolecular structure with a hollow interior of a specific volume. Thisinternal cavity, which is lipophilic (i.e., is attractive to hydrocarbonmaterials when compared to the exterior), is a key structural feature ofthe cyclodextrin, providing the ability to complex molecules (e.g.,aromatics, alcohols, halides and hydrogen halides, carboxylic acids andtheir esters, etc.). The complexed molecule must satisfy the sizecriterion of fitting at least partially into the cyclodextrin internalcavity, resulting in an inclusion complex.

CYCLODEXTRIN TYPICAL PROPERTIES CD PROPERTIES α-CD β-CD γ-CD Degree ofpolymerization 6 7 8 (n =) Molecular Size (A°) inside diameter 5.7 7.89.5 outside diameter 13.7 15.3 16.9 height 7.0 7.0 7.0 Specific Rotation[α]²⁵D +150.5 +162.5 +177.4 Color of iodine complex Blue YellowYellowish Brown Solubility in Distilled water 14.50 1.85 23.20 (g/100mL) 25° C.

The oligosaccharide ring forms a torus, as a truncated cone, withprimary hydroxyl groups of each glucose residue lying on a narrow end ofthe torus. The secondary glucopyranose hydroxyl groups are located onthe wide end. The parent cyclodextrin molecule, and useful derivatives,can be represented by the following formula (the ring carbons showconventional numbering) in which the vacant bonds represent the balanceof the cyclic molecule:

The CD's internal cavity size (i.e., α, β, γ) can be considered and thefunctional group modification can be suitable for changing the desiredbulk polymer and surface polymer characteristics in addition to formingan inclusion complex with targeted volatiles or impurities. To achieve aspecific result, more than one cavity size and functional group may benecessary.

According to the present disclosure, the cyclodextrin (CD) is a compoundsubstantially free of an inclusion complex. As applied in thisdisclosure, the term “substantially free of an inclusion complex” meansthat the quantity of the CD in the bulk polymer contains a largefraction having CD free of a polymer contaminant in the central pore ofthe cyclodextrin ring (see FIGS. 1A, 1B and 1C). The central pore isused as a binding location for permeants. Upon use, the central pore canacquire a permeant or other inclusion compound. However, some complexingcan occur before use, for example, during manufacture. This complexingcan occur as residual polymer impurities and degradation materialsbecome available for inclusion into the CD cavity for complexation.

CD molecules have available for reaction with a functionalizedpolyolefin the primary hydroxyl at the six position of the glucosemoiety, and at the secondary hydroxyl in the two and three positions.Because of the geometry of the CD molecule, and the chemistry of thering substituents, all hydroxyl groups are not equal in reactivity.However, with care and effective reaction conditions, dry CD moleculescan be reacted to obtain grafted CD. CD with selected substituents (i.e.substituted only on the primary hydroxyl or selectively substituted onlyat one or both the secondary hydroxyl groups) can also be grafted ifdesired. Directed synthesis of a derivatized molecule with two differentsubstituents or three different substituents is also possible. Thesesubstituents can be placed at random or directed to a specific hydroxyl.Further, CD alcohol derivatives (e.g., hydroxyethyl and hydroxypropyl)and amino derivatives can be reacted to make a grafted CD.

The preferred preparatory scheme for producing a grafted CD polyolefinmaterial having compatibility with polyolefin resin involves reactionsat the primary or secondary hydroxyls of the CD molecule. It is meantthat a hydroxyl functionality of the CD reacts with the anhydride orepoxide component of the functionalized polyolefin to form a reactionproduct. The formation of an ester or ether bond on either the primaryor secondary ring hydroxyls of the CD molecule involve well-knownreactions. Further, CD having less than all of available hydroxylssubstituted with derivative groups can be grafted with one or more ofthe balance of the available hydroxyls. The primary —OH groups of thecyclodextrin molecules are more readily reacted than the secondarygroups. However, the molecule can be substituted on virtually anyposition to form useful compositions. Broadly, we have found that a widerange of pendant substituent moieties can be used on the molecule. Thesederivatized cyclodextrin molecules can include alkylated cyclodextrin,hydrocarbyl-amino cyclodextrin, and others. The substituent moiety mustinclude a region that provides compatibility to the derivatizedmaterial.

Amino and azido derivatives of cyclodextrin having pendent thermoplasticpolymer containing moieties can be used in the sheet, film or containerof the invention. The sulfonyl derivatized cyclodextrin molecule can beused to generate the amino derivative from the sulfonyl groupsubstituted cyclodextrin molecule via nucleophilic displacement of thesulfonate group by an azide (N₃ ⁻¹) ion. The azido derivatives aresubsequently converted into substituted amino compounds by reduction.Such derivatives can be manufactured in symmetrical substituted aminegroups (those derivatives with two or more amino or azido groupssymmetrically disposed on the cyclodextrin molecule or as asymmetrically substituted amine or azide derivatized cyclodextrinmolecule. Due to the nucleophilic displacement reaction that producesthe nitrogen containing groups, the primary hydroxyl group at the6-carbon atom is the most likely site for introduction of anitrogen-containing group. Examples of nitrogen containing groups thatcan be useful in the invention include acetylamino groups (—NHAc),alkylamino including methylamino, ethylamino, butylamino, isobutylamino,isopropylamino, hexylamino, and other alkylamino substituents. The aminoor alkylamino substituents can further be reactive with other compoundsthat react with the nitrogen atom to further derivatize the amine group.Other possible nitrogen containing substituents include dialkylaminosuch as dimethylamino, diethylamino, piperidino and piperizino.

The cyclodextrin molecule can be substituted with heterocyclic nucleiincluding pendent imidazole groups, histidine, imidazole groups,pyridino and substituted pyridino groups.

Thermoplastic Resins

Polyolefins such as polyethylene and polypropylene can be use in theinvention as well as copolymers of ethylene propylene and other alphaolefin monomers.

Commercial polyolefin functionalization is achieved using solution, meltand solid state routes known in the art. The process covalently bondsmonomers onto vinyl polymers or onto polyolefin polymers includingcopolymers of olefins with other monomers, such as vinyl monomers, whichpredominately constituent the olefin portion. Polyolefins useful inmodified or un-modified embodiments according to the disclosure includepoly(ethylene) or PE, poly(propylene) or PP, poly(ethylene-co-propylene)or PEP, ethylene/methyl acrylate copolymer, and ethylene/ethyl acrylatecopolymer. The polyolefins can be functionally modified with unsaturatedcompounds such as unsaturated anhydrides and carboxylic acids. Anypackaging grade of a vinyl polymer can be used.

Melt flow index or melt flow rate of a thermoplastic material, includingboth a polyethylene and a polypropylene can be measured in accord withASTM method D1238. This test method obtains a measurement of the rate ofextrusion of molten resins at a defined temperature and through astandard die under specific weight conditions using a piston drivenplastometer device as defined in the method. Each class thermoplasticpolymer (e.g.) polyethylene, polypropylene, polyacrylic, polyester,polyvinyl chloride etc., has a established and defined set oftemperature and weight parameters. The melt flow rate or melt index havebeen used for many years to approximate molecular weight. Molecularweight varies inversely to melt flow index or melt flow rate. As themelt flow rate increases, the molecular weight is known to decrease. Forpolyethylene the standard conditions are 190° C. and 2.16 kG. Forpolypropylene the standard conditions are 230° C. and 2.16 kG.

Polyolefin and functionalized polyolefins have extensive industrialapplications such as coextrusion tie resins in multi-layer films andbottles for the food industry, compatibilizers for engineering polymersand plastic fuel tank tie resins for the automotive industry,flexibilization and compatibilization of halogen free polymers forcables and for filler materials used in roofing construction.Functionalized polyolefins can also find application in containers forfood contact. Functionalized polyolefins useful in the presentdisclosure are maleated polyethylene and polypropylene (OREVAC™ andLOTRYL™ available from Arkema, Philadelphia, Pa., PLEXAR® resinsavailable from EQUISTAR, Rotterdam, The Netherlands, ADMER® resin fromMitsui Chemicals, Tokyo, Japan, FUSABOND® resins from DuPont,Wilmington, Del., OPTIM™ resins from MÂNAS, India and EXXELOR™ fromExxon/Mobil, Houston, Tex.), functionalized EP, EVA and EPDM (such asethylene-propylene-butadiene or, ethylene-propylene-1,4-hexadienepolymers) ethylene-octene copolymers, ethylene-n butyl acrylate-maleicanhydride, ethylene-ethylacrylate-maleic anhydride terpolymers andcopolymers of ethylene-glycidyl methacrylate and the like. Theethylene-propylene-1,4-hexadiene copolymer can be represented as:

wherein x is selected to obtain about 70 to 90 wt % ethylene, y isselected to obtain about 10 to 30 wt % propylene and z is selected toobtain up to about 5 wt % 1,4-hexadiene. The vacant bonds are linked tosimilar groups, H, or end groups.

Other polyolefins can be used in compositions of the present which areknown in the art to impart desirable processing or end productcharacteristics. For example, polybutene can be added to increase fiberstrength. Other olefins that can be added to produce copolymers orblends include alpha olefins such as 1-hexene and 1-octene to impartflexibility.

Compositions in accordance with the present disclosure can be preparedusing reactive extrusion by feeding a dry cyclodextrin, or derivativethereof, (<0.10% moisture), a functionalized polyolefin and optionally asecond polyolefin, into an extruder at temperatures such that thecyclodextrin reacts with the functionalized polyolefin as the moltenpolymer and cyclodextrin are transported through the extruder to form areaction product containing, for example, an ester group whichcovalently bonds the cyclodextrin to the polyolefin. The ratio offunctionalized polyolefin to non-functionalized polyolefin can beadjusted for a specific application and conversion process.

The present invention is directed to a stoichiometric reaction productof a cyclodextrin and a graft linking agent (i.e., anhydride, epoxide,etc.), and a non-volatile and polymer compatible carboxylic acid,resulting in a modified polymer especially suited as a masterbatch whichcan be subsequently let down with one or more non-functionalizedthermoplastic polymers and thermoplastic elastomers at a weight ratio ofone (1) parts of the masterbatch composition to ten (10) to twenty (20)parts of non-functionalized polymer. In other words the blend of polymerand master batch, or functionalized polymer, after blending can containabout 0.01 to 10 wt % of the CD functionalized polymer, in certainapplications the polymer can contain about 0.02 to 8 wt % of thefunctionalized material, about 0.02 to 5 wt % of the functionalizedmaterial or about 0.02 to 2 wt % of the functionalized material. Amaleic acid, fumaric acid or maleic anhydride functionalized material isuseful for bonding CD to the polyolefin. The stoichiometric ratio formelt grafting is calculated on a gram-mole (gram-formula-weight) basiswhere one (1) gram-mole of CD (+, β or γ form) is equivalent to one (1)gram-mole the grafted anhydride, glycidyl and carboxylic acid moiety.

EXAMPLES Spunbond Fiber Production

Spunbond webs were produced with fatty acids and fatty acid derivativesfor analyzing processability and neutralization of ammonia and volatileamine compounds. A Nordson Fiber Systems/Hill Inc. Bicomponent spunbondSystem was used with a die orifice diameter of 0.35 mm and a capillaryratio of 4:1. The quenching distance was 41 cm, with a spinning distanceof 60 cm, and forming distance of 75 cm. This configuration produced twodenier fiber (18 u); 20 gms per square meter web. The BicomponentSpunbond line was configured to extrude different melt streams into theCore and Sheath. Only in the case of Example 6 is the core and sheathformulation different. All formulation with the exception of ComparativeExample C1 were made by adding a concentrate (masterbatch) containingthe fatty acid, polybutene, MA/PP and homopolymer PP at a ratio of 15parts concentrate to 85 parts PP homopolymer

Example 1 Spunbond Fiber; 93.25% PP Homopolymer, 2.1% Polybutene, 3.9%MA/PP 0.75% Oleic Acid. Some Smoking Example 2 Spunbond Fiber; 93.25% PPHomopolymer, 2.1% Polybutene, 3.9% MA/PP 0.75% Stearic Acid. SomeSmoking Example 3 Spunbond Fiber; 93.25% PP Homopolymer, 2.1%Polybutene, 3.9% MA/PP (High MA Content), 0.75% Octadecenyl SuccinicAnhydride. Low Smoking Example 4 Spunbond Fiber; 93.25% PP Homopolymer,2.1% Polybutene, 3.9% MA/PP (High MA Content), 0.75% Sebacic Acid. HeavySmoking Example 5 Spunbond Fiber; 93.25% PP Homopolymer, 2.1%Polybutene, 0.0% MA/PP, 0.75% Stearic Acid. Heavy Smoking Example 6Spunbond Fiber; 93.25% PP Homopolymer, 2.1% Polybutene, 3.9% MA/PP (HighMA Content) Sheath: 0.75% Octadecenyl Succinic Anhydride; Core: 0.75%Sebacic Acid. Low Smoking Example 7 Spunbond Fiber; 91.75% PPHomopolymer, 2.1% Polybutene, 3.9% MA/PP (High MA Content), 1.5% AlphaCD, 0.75% Octadecenyl Succinic Anhydride. Comparative Example C1Spunbond Fiber 100% PP Homopolymer. No smoking Comparative Example C2Spunbond Fiber; 88.45% PP Homopolymer, 10.05% MA/PP (low MA Content),1.5% Alpha CD Comparative Example C3 Spunbond Fiber, 92.5% PPHomopolymer, 2.1% Polybutene, 3.9% MA/PP (High MA Content), 1.5% AlphaCD

When fatty acids are incorporated into Polypropylene and extruded intofiber some of the fatty acid volatilizes at 240° F. (the temperature ofthe molten PP when it exits the die) the fatty acids quickly condense asthe temperature of the air decreases as it is pulled away by theexhaust.

Headspace Ammonia Analysis

Samples were prepared by placing about 0.670 g fiber swatches into 250mL jars (1-Chem item #S121-0250, tall clear WM Septa-Jar™,Fisher-Scientific P/N 05-719-452) equipped with “TEFLON™” faced septa(available from Fisher Scientific P/N 14-965-84). Empty calibrationstandards jars and sample jars were equilibrated at 38° F. An ammoniumhydroxide solution of about 2.9-7.6 wt % was made by dilutingconcentrated ammonium hydroxide (ACS reagent, 28.0-30.0% as NH₃,Sigma-Aldrich P/N 221228 or equivalent) 2:5-1:10 with deionized water.Jars were inoculated with 10 μL of ammonia solution by removing the jarcap and injecting the ammonia aliquot onto the interior side of the jar.Care was taken to avoid contact of the solution with the non-wovensample and to quickly replace and seal the cap. The jars were thenreturned to the 38° F. oven and removed for evaluation after 30 minutes.It is crucial that the inoculation process and the timing be carried outidentically for all samples. 2, 4, 6, 8 and 10 μL aliquots of theammonia solution were inoculated into empty jars as standards. Groups of2-3 jars were inoculated at one time and then returned to the 38° F.chamber for 30 minutes.

40 mL of headspace was extracted by a graduated glass gas-tight syringe(Fisher-Scientific P/N SG-009660 or equivalent) from the jar headspacebelow the septum of the jars and slowly bubbled into 5 cc of DI water todissolve the gas phase ammonia. The resulting ammonia solution wastitrated to a phenolphthalein endpoint using a graduated 1000 μL syringewith 0.001-0.004 M HCl. The amount of free ammonia present in the jarswas then calculated by using a calibration curve from the standards.

TABLE 1 Static Headspace Ammonia Test Summary NH₃ μg NH₃ sorbed % ofChallenged Challenge Std sorbed/g fiber Example Description (μg) Ave.Dev. Ave. Std. Dev. C1 Control PP Fiber 1044 80.4 14..2 7.7 1.4 Ex 10.75% Oleic 1044 797.9 112.6 76.4 10.8 Ex 2 0.75% Stearic 1044 889.598.2 85.2 9.4 Ex 3 0.75% ODSA 1044 852.5 24.9 81.7 2.4 Ex 4 0.75%Sebacic 1044 896.1 48.1 85.8 4.6 Ex 5 0.75% Stearic (no 1044 755.2 97.972.3 9.4 graft Ex 6 0.75% ODSA sheath 1044 992.3 117.9 95.1 11.3 Sebaciccore Ex 7 1.5% CD containing 1044 839.6 58.9 80.4 5.6 0.75% ODSA C2 1.5%CD 1044 127.0 26.1 12.2 2.5 Low MA C3 1.5% CD 1044 130.6 16.6 12.5 1.6High MAFormulation C2 is produced with a MAPP that contains approximately 1%Maleic Anhydride. All other formulations employ a MAPP with greater then2% Maleic Anhydride.

TABLE 2 Comparative Examples MB C2-MB C3 and Examples 8 wt % MAPP (wt %maleic anhydride Cyclodextrin Polybutene Masterbatch content) (wt %) PP(wt %) (wt %) ODSA (wt %) MB-C2 67 (1.1) 10 23 N/A* N/A MB-C3 26 (3.0)10 40 14 N/A MB-8 26 (3.0) 10 45 14 5 *N/A indicates none added

Each of the masterbatch formulas listed in Table 3 was then blended withPP at a ratio of 15/85 (wt/wt) and spunbond fiber was produced with adiameter in the range of 17-20 microns

The Headspace Ammonia Analysis described above was followed with theexception that 1 g of spunbond fiber was placed in the 250 mL jars.

Spunbond fibers of Comparative Examples C2 and C3 removed 0.100-0.150 ugof ammonia, an efficiency of about 35%. Spunbond fibers of Example 7removed 0.840 mg of ammonia, an efficiency of 75%.

All of the fatty acids tested have similar performance on aweight/weight basis. Under test conditions, the difference in the numberof acid groups between the di-acids and mono-acids has little effectupon the efficiency of removal of NH₃ from the headspace.

Seventeen gram samples of fiber from, Examples C1,2,3, and 5 wereextracted with 800 ml of a 0.05 Normal NH₃ in 5% ethanol solution for 60minutes to solublize the available organic acids on the surface of thefiber. The weight of the dried extract minus the weight of the controlextract was taken to be the Ammonium salt of the fatty acid.(diacids).The results of the fiber extraction can be found in the table below.

TABLE 3 Percent of acid Sample Description Fiber weight Dried Extractextracted C1 Control PP 34.10 0.0044 NA Ex 2 Stearic Acid 33.44 0.01624.7 Ex 3 ODSA 33.90 0.0152 4.25 Ex 5 Strearic Acid 33.62 0.0314 10.71 noMAPPWith less then 5% of the fatty acids (anhydrides) in the fiber it isexpected that the efficiency of the fatty acid addition the fiber wouldbe similar to that of the MAPP fiber and the reduction in Ammonia wouldbe in the order of 500 ug per gram of Fiber. However, surprisingly theamount of ammonia reduction is nearly double the expected value despitethe small amount of fatty acid on the surface of the fibers. Despite thefact that a large portion of the fatty acids are not on the surface theyare still capable of removing ammonia from the headspace to a muchgreater efficiency then the MAPP alone. Additionally, performancetesting comparison of the treated and control samples of nonwoven fabricproduct samples was conducted. This testing involved paired comparisonevaluation of both samples challenged with an ammonia/urine solution.The samples were evaluated with a trained and an untrained panel ofassessors. The testing results from both sensory panels show the ammoniaand urine character and overall odor perceived in the treated samples issignificantly lower than that perceived in the control samples.

In the detailed testing, the primary sample for testing was called:

Example 7, Spunbond PP Grafted α-CD+ODSA with 0.5% hydrophilic surfacetreatment

, the control sample provided was called:

Comparative Example C1, Spunbond PP Control with 0.5% hydrophilicsurface treatment.

The testing objective was to document that when exposed to anammonia/urine solution, the treated sample of nonwoven fabric reducesthe odor intensity more than the control sample. A small volume of anammonia/urine solution was placed in the bottom of glass jars lined withthe fabric samples. The samples were heated and evaluated to determinewhich of the two samples had lower odor intensity. The assessors alsoreported odor descriptor terms noticed in the samples.

ASTM International E2164-01, Standard Test Method for DirectionalDifference Test, was used to evaluate if the treated sample had thelower odor intensity. The general nature of this standard is to presenttwo samples to an assessor and have them determine a difference betweenthe samples based on one attribute/parameter (paired comparison). Thenumber of assessors needed for the test is dependent on the chosenstatistical power.

For this test, it was determined that a Type I error of 5% (α=0.05) wasacceptable, which refers to 5% risk that a difference exists when onedoes not. Additionally, a Type II error of 30% (β=0.30) was acceptable,which refers to a 30% risk that there is no difference when thereactually is one. A high level of Type II risk is acceptable, since thisfavors the control sample. Finally, a PMAX value of 75% was used, theproportion of common responses that we want to test against. In otherwords, the results of the test will provide evidence that more than 75%of the population will detect a difference in the samples above thelevel of chance alone.

ASTM E2164 provides look-up tables to determine the number of assessorsneeded for these statistical parameters. A one-tailed test was usedsince the treated sample was expected to be lower in odor intensity;therefore, it was determined from the standard that a minimum of 18assessor responses are necessary.

The ammonia solution used for this testing was prepared by placing1.6-mL of a 29% ammonium hydroxide solution into 100-mL of deionizedwater. The solution was well mixed. This ammonia solution was then usedto reconstitute freeze-dried urine (KOVA-Trol II Low Abnormal HumanUrinalysis Control; HYCOR Biomedical, Inc.). This freeze-dried urine wasreconstituted with 30-mL of the ammonia solution. The urine is normallyreconstituted with 60-mL of water, so the ammonia solution was used toincrease the ammonia odor of the urine and only 30-mL was used toprovide a more concentrated urine.

Samples were prepared with 4.5″×6″ swatches of the fabric samples liningthe wall of 250 mL glass jars (4.5″ tall, 6″ circumference) with Teflonlined lids. The samples were coded with three digit randomly generatednumbers labeled on the jar lids. The covered jars were preheated in a38° C. oven for 30 minutes. Next, an auto-pipette was used to place 10μL, of the ammonia/urine solution in the bottom of the jar. Care wastaken not to contact the fabric directly with the solution. The jar wascapped and placed back in the oven at 38° C. and presented to theassessors for observation after 30 minutes. The entire 10 μL of solutionevaporated to provide an ammonia concentration of approximately 250-ppm.

An initial test was done of the fabric samples utilizing thirteenassessors trained and experienced in sensory evaluation of products andmaterials. The assessors have previously been trained to various sensorytesting methodologies including threshold testing, scaling,discrimination techniques, and the application of various attributeratings. Each assessor was presented two pairs of the treated andcontrol samples. The pairs of samples was presented with random orderpresentation for a balanced design so each sample type appeared firstand second in sequence an equal number of times.

The presentations were conducted independently with different samplecoding for each pair. The assessors received the first pair immediatelyafter they were removed from the oven. The assessors removed the lid ofthe first jar sample and immediately sniffed the sample with their nosenear the jar opening. The assessors were instructed to take as much timeas they felt necessary to rest their nose before sniffing the secondsample. This was usually a rest period of about 30-60 seconds. Theassessor repeated the observation with the second jar. The testquestionnaire asked the assessor to report which of the samples had “thelower odor intensity.”

After completing this first observation, the jars were removed from thetesting room and the lids were replaced with lids labeled with differentcodes. The jars were held for two-minutes and returned to the assessors.The assessors repeated the evaluation to determine which sample waslower in odor intensity and they were asked to complete characterprofiling questionnaires for each sample. They had been providedinstruction for this ahead of time, so they were aware they needed to beobservant of specific descriptors when evaluating the second set ofsamples. For each sample, the assessors reported the hedonic tone, theodor character descriptors observed, and the relative strength of mainodor character and sensation (feeling) categories.

Hedonic tone is a measure of the pleasantness or unpleasantness of anodor. This is a subjective test parameter where assessors use a scale of−10 (most unpleasant) to +10 (most pleasant) to report their perceptionof the odor. A score of zero is a neutral odor. The hedonic tone valuesprovided by the trained assessors should not be considered to representthe opinions of the general population. The values should be used forcomparison of the pleasantness between samples since they were observedby the same panel of assessors.

Assessors report the odor descriptors they notice by marking characterson a standard computerized scoring sheet. The odor characters areorganized into eight main categories: vegetable, fruity, floral,medicinal, chemical, fishy, offensive, and earthy. When a descriptorterm is assigned to an odor, the main odor descriptor categories can berated in relative strength on a 1 to 5, faint to strong, scale (0=notpresent). The odor testing descriptor data is then plotted on a spiderplot (radar plot) format with the distance along each axis representingthe 0-5 scale for each of the categories. The plot creates a “pattern”that can be readily compared to spider plots for other samples.Furthermore, specific odor descriptors are presented in a histogramwhere each reported descriptor is listed along with the percent ofreporting assessors.

The Trigeminal Nerve (Fifth Cranial Nerve), located throughout the nasalcavity and the upper palate, and other nerves sense the presence of someodors (i.e. “feels like.” rather than “smells like.”). Eight (8) commonsensation descriptors that can be used include: itching, tingling, warm,burning, pungent, sharp, cool, and metallic. Again, assessors can ratethe strength of the presence of these attributes on a 0 to 5 scale andthe results then plotted on a spider plot.

After completing the character profiling, a second set of samples wasremoved from the oven and presented to the assessors to determine whichhad lower odor intensity.

A second test was conducted with a consumer panel of untrainedassessors. Twenty assessors were selected from the general population.The assessors were over 18 years of age and nonsmokers.

Each assessor was presented the two pairs of samples two times with theorder of presentation randomized so each sample was presented first andsecond in sequence an equal number of times. Each pair was independentlycoded, so the assessors did not know they were the same pair of samples.For each pair, the questionnaire asked the assessor to report whichsample had “the lower odor intensity.” After observing the set ofsamples a second time, the assessors were asked to report the presenceof ten odor descriptor terms in each sample by checking a box if theywere present. The ten descriptor terms were: floral, vegetable, earthy,musty, sulfurous, fishy, chemical-like, urine, ammonia, and medicinal.The assessors were also allowed to report “other” and write in their ownterms.

Results Trained Panel

For the thirteen trained assessors, in the first round of the paircomparison testing, 13 of the 13 assessors selected the treated sample(Example 7) as having the lower odor intensity. In the second round ofobserving the same samples, 11 of the 13 selected this treated sample ashaving the lower intensity.

In the second set of pairs, 12 of the 13 assessors selected the treatedsample (Example 7) as having lower odor intensity.

Overall, for the first round of evaluating the samples, this is 25 ofthe 26 observations identifying the treated sample as lower intensity.Of all samples, this is 36 of the 39 observations identifying thetreated samples as lower intensity. Table 3 in ASTM E2164 provides thenecessary number of responses for a statistically significant result fora one tailed test based on the Type I error and the number of assessorsused. This table shows that if 10 or more of 13 assessors identify thetreated sample as lower odor intensity, then this would be astatistically significant result. Therefore, the eleven to thirteenselections for all tests provides evidence at the 95% level that thepopulation would be able to detect the treated sample as providing alower odor intensity. Taking into account the results of the three setsof observations, the 25 of 26 identifications and the 36 of 39identifications are greater than 99.9% confidence that the treatedsample would be identified as having lower odor intensity.

The average hedonic tone values provided by the trained assessors were−1.6 for the treated sample (Example 7) and −4.9 for the control sample(Comparative Example C1). The treated sample would be considered to bemore neutral (closer to zero), though it is towards the unpleasant sideof the scale. The hedonic tone value of the control sample suggests itwas very unpleasant. The values were found to be statistically different(p<0.0001, α=0.05).

The odor descriptor terms provided by the assessors included earthy,stale, offensive, and musty for the treated sample and ammonia, urine,offensive, and musky for the control sample. Earthy characters had thehighest frequency of reporting for the treated sample. Medicinal,including ammonia, and offensive, including urine, had the highestfrequency of reporting for the control sample.

FIG. 1 provides a summary of the relative strength ratings of the odorcharacter categories. The control sample had the highest relativestrength and greatest difference compared to the treated samples formedicinal and offensive characters. The treated sample was slightlyhigher than the control in earthy

FIG. 2 provides a summary of the relative strength of odor sensations(feelings). The control samples had the highest relative strength andgreatest difference from the treated samples for burning, pungent, andsharp categories. The only sensations reported for the treated samplewas light pungent and warm, which was at the identical relative strengthlevel of the control sample and is likely due to the fact the sampleswere presented to the assessors within minutes of being removed from the38° C. oven. For the untrained assessors, in the first round of the paircomparison testing, 17 of the 20 assessors selected the treated sampleas having the lower odor intensity. In the second presentation of thefirst pair of samples, 16 of the 20 assessors selected the treatedsamples as having lower odor intensity. In the second set of samples, 19of the 20 assessors selected the treated sample as lower odor intensityin the first observation. In the second presentation of the second pair,15 of the 20 assessors selected the treated sample as lower odorintensity.

Overall, in the first observations of the two sets of samples, this is36 of 40 observations identifying the treated samples lower in odorintensity. In observing the samples the second time, 31 of the 40observations identified the treated samples as lower in odor intensity.

Reviewing the results of each round, we can be at least 95% confidentthat the population would be able to detect the treated sample asproviding lower odor intensity. The 36 of 40 and 31 of 40 responses inboth rounds combined provides 99.9% confidence level that the populationwill detect the treated sample as having a lower odor intensity. Theconsumer panel also recorded the odor descriptors they noticed in thesecond observation of each set of samples. In the first set of samples,30% of assessors reported ammonia and urine character in the controlsample and only 15% reported these characters present in the treatedsample. Earthy and musty were noticed most frequently in both samples.In the second set of samples, 40% reported ammonia and 20% reportedurine in the control sample and 5% reported these characters in thetreated sample. Again, earthy and musty were noticed most frequently.

The directional difference (paired comparison) testing of Treated SampleExample 7 compared to Control Sample Comparative Example C1 documentedthat the treated fabric reduced ammonia and urine odors more than thecontrol fabric.

The results of the panel of trained sensory assessors show that atgreater than the 99% confidence level the population would notice thetreated fabric reduces the odor more than the control. The trainedassessors found the hedonic tone of the control sample to besignificantly more unpleasant than the treated sample. These trainedassessors also reported the control sample had a higher level ofmedicinal and offensive odors and a higher level of sharp and pungentsensations.

The results from the consumer sensory panel (untrained assessors) alsoshows that at greater than 99% confidence level the general populationwould notice the treated fabric reduces the odors more than the control.These assessors also noticed the control sample odors contained moreammonia and urine odors than the treated sample, while both had earthyand musty odors.

Various modifications and alterations of the embodiments and examples inaccordance to the invention will become apparent to those skilled in theart without departing from the scope and spirit of the disclosure, andit should be understood that this disclosure is not to be unduly limitedto the illustrative embodiments and examples set forth herein.

1. A thermoplastic polymer composition, comprising (i) a blend of: (1) amajor proportion of a polyolefin resin and (2) about 1 wt % to 47 wt %of a modified polyolefin resin, and (ii) from about 0.1 wt % to about 5wt % of a non-volatile and polymer compatible carboxylic acid based onthe polymer composition.
 2. The thermoplastic polymer composition ofclaim 1 wherein the non-volatile and polymer compatible carboxylic acidis a C₈ to C₅₀₀ carboxylic acid and the carboxylic acid comprisesbetween about 0.25 wt % to about 2.5 wt % based on the polymercomposition.
 3. The thermoplastic polymer composition of claim 1 whereinthe non-volatile and polymer compatible carboxylic acid is a C₈ to C₂₀₀dicarboxylic acid and the dicarboxylic acid comprises between about 0.25wt % to about 2.5 wt % based on the polymer composition.
 4. Thethermoplastic polymer composition of claim 3 wherein the dicarboxylicacid is an acid anhydride and comprises between about 0.25 wt % to about2.5 wt % based on the polymer composition.
 5. The thermoplastic polymercomposition of claim 3 wherein the dicarboxylic acid is a C₈ to C₂₈alkenyl substituted succinic acid or anhydride and comprises betweenabout 0.5 wt % to about 1.5 wt % based on the polymer composition. 6.The thermoplastic polymer composition of claim 5 wherein thedicarboxylic acid is an octadecenyl substituted succinic acid oranhydride and comprises between about 0.5 wt % to about 1.5 wt % basedon the polymer composition.
 7. The thermoplastic polymer composition ofclaim 1 comprising about 1 to 50 wt % of the polyolefin resin and about0.01 to about 15 wt % of the modified polyolefin; wherein the polyolefincomprises a melt index of about 0.5 to 1500 g-10 min⁻¹ and the modifiedpolyolefin is derived from a polyolefin having a melt index of about 0.7to 800 g-10 min.⁻¹
 8. The thermoplastic polymer composition of claim 1wherein the polyolefin comprises a polyethylene and the modifiedpolyolefin comprises a cyclodextrin-modified polyethylene.
 9. Thethermoplastic polymer composition of claim 1 wherein the polyolefincomprises a polypropylene and the modified polyolefin comprises acyclodextrin-modified polypropylene.
 10. The thermoplastic polymercomposition of claim 1 wherein the polyolefin comprises apoly(ethylene-co-propylene) and the modified polyolefin comprises acyclodextrin-modified poly(ethylene-co-propylene).
 11. The thermoplasticpolymer composition of claim 1 wherein the modified polyolefin comprisesa cyclodextrin bonded to a maleic anhydride modified polyolefin whereinthe polyolefin comprises about 0.05 to about 5 weight percent maleicanhydride.
 12. The thermoplastic polymer composition of claim 1 whereinthe modified polyolefin comprises a cyclodextrin-modified high-densitypolyethylene.
 13. The thermoplastic polymer composition of claim 12wherein the cyclodextrin modified polyolefin resin comprises apolymethylene backbone having randomly substituted covalently bondedgroups derived from a cyclodextrin compound, wherein the compositioncomprising about 100 parts by weight of the polyolefin resin and about0.01 to 50 parts by weight of the modified polyolefin; wherein thecyclodextrin compound is substantially free of a compound in the centralpore of the cyclodextrin ring.
 14. A fiber, comprising the compositionof claim
 1. 15. The fiber of claim 14 having a diameter of about 0.2 to50 microns.
 16. The fiber of claim 14 wherein the carboxylic acid is aC₈ to C₂₀₀ dicarboxylic acid and the dicarboxylic acid comprises betweenabout 0.25 wt % to about 2.5 wt % based on the polymer composition. 17.The fiber of claim 16 wherein the fiber is a component of a woven ornonwoven fabric.
 18. The fiber of claim 16 wherein the dicarboxylic acidis a C₈ to C₂₈ alkenyl substituted succinic acid or anhydride.
 19. Thefiber of claim 18 wherein the dicarboxylic acid is an octadecenylsubstituted succinic acid or anhydride.
 20. The fiber of claim 14comprising about 48 to 94 wt % of the polyolefin resin and about 0.25 toabout 2.5 wt % of the carboxylic acid; wherein the polyolefin comprisesa melt index of about 0.5 to 1500 g-10 min⁻¹ and the modified polyolefinis derived from a polyolefin having a melt index of about 0.7 to 800g-10 min.⁻¹
 21. The fiber of claim 14 wherein the polyolefin comprises apolyethylene and the modified polyolefin comprises acyclodextrin-modified polyethylene.
 22. The fiber of claim 14 whereinthe polyolefin comprises a polypropylene and the modified polyolefincomprises a cyclodextrin-modified polypropylene.
 23. The fiber of claim14 wherein the polyolefin comprises a poly(ethylene-co-propylene) andthe modified polyolefin comprises a cyclodextrin-modifiedpoly(ethylene-co-propylene).
 24. The fiber of claim 14 wherein themodified polyolefin comprises a cyclodextrin bonded to a maleicanhydride modified polyolefin wherein the polyolefin comprises about0.05 to about 5 weight percent maleic anhydride.
 25. The fiber of claim14 wherein the modified polyolefin comprises a cyclodextrin-modifiedhigh-density polyethylene.
 26. The fiber of claim 25 wherein thecyclodextrin compound comprises a modified polyolefin resin comprising apolymethylene backbone having randomly substituted covalently bondedgroups derived from a cyclodextrin compound, the composition comprisingabout 100 parts by weight of the polyolefin resin and about 0.01 to 50parts by weight of the modified polyolefin; wherein the cyclodextrincompound is substantially free of a compound in the central pore of thecyclodextrin ring.
 27. A thermoplastic polymer masterbatch, comprising(i) a blend of a major proportion of a polyolefin resin; and (ii) fromabout 1 wt % to about 15 wt % a non-volatile and polymer compatiblecarboxylic acid based on the polymer composition.
 28. The thermoplasticpolymer masterbatch of claim 27 wherein the non-volatile and polymercompatible carboxylic acid is a C₈ to C₄₀ carboxylic acid and thecarboxylic acid comprises between about 1 wt % to about 15 wt % based onthe polymer masterbatch.
 29. The thermoplastic polymer masterbatch ofclaim 27 wherein the non-volatile and polymer compatible carboxylic acidis a C₈ to C₄₀ dicarboxylic acid and the dicarboxylic acid comprisesbetween about 1 wt % to about 15 wt % based on the polymer masterbatch.30. The thermoplastic polymer masterbatch of claim 29 wherein thenon-volatile and polymer compatible dicarboxylic acid is an acidanhydride and the acid anhydride comprises between about 1 wt % to about15 wt % based on the polymer masterbatch.
 31. The thermoplastic polymermasterbatch of claim 29 wherein the dicarboxylic acid is an alkenylsubstituted succinic acid or anhydride.
 32. The thermoplastic polymermasterbatch of claim 31 wherein the diacid is an octadecenyl substitutedsuccinic acid or anhydride.
 33. The thermoplastic polymer masterbatch ofclaim 27 comprising about 10 to 70 wt % of the polyolefin resin, about10 wt % to about 45 wt % of a modified polyolefin resin, and about 1 to15 wt % weight of the carboxylic acid; wherein the polyolefin comprisesa melt index of about 0.5 to 1500 g-10 min⁻¹ and the modified polyolefinis derived from a polyolefin having a melt index of about 0.7 to 800g-10 min.^(−1.)
 34. The thermoplastic polymer masterbatch composition ofclaim 27 wherein the polyolefin comprises a polyethylene and themodified polyolefin comprises a modified polyethylene.
 35. Thethermoplastic polymer masterbatch composition of claim 27 wherein thepolyolefin comprises a polyethylene and the modified polyolefincomprises a modified polypropylene.
 36. The thermoplastic polymermasterbatch composition of claim 27 wherein the polyolefin comprises apolypropylene and the modified polyolefin comprises a modifiedpolypropylene.
 37. The thermoplastic polymer masterbatch composition ofclaim 27 wherein the polyolefin comprises a poly(ethylene-co-propylene)and the modified polyolefin comprises a modifiedpoly(ethylene-co-propylene).
 38. The thermoplastic polymer masterbatchcomposition of claim 27 wherein the polyolefin comprises apoly(ethylene-co-propylene) and the modified polyolefin comprises amodified polypropylene.
 39. The thermoplastic polymer masterbatchcomposition of claim 27 wherein the modified polyolefin comprises acyclodextrin bonded to a maleic anhydride modified polyolefin whereinthe polyolefin comprises about 0.05 to 5 weight percent maleicanhydride.
 40. The thermoplastic polymer masterbatch composition ofclaim 27 wherein composition further includes a polymer compatiblecyclodextrin compound.
 41. The thermoplastic polymer composition ofclaim 38 wherein the cyclodextrin compound comprises a modifiedpolyolefin resin comprising a polymethylene backbone having randomlysubstituted covalently bonded groups derived from a cyclodextrincompound, the composition comprising about 100 parts by weight of thepolyolefin resin and about 0.01 to 50 parts by weight of the modifiedpolyolefin; wherein the cyclodextrin compound is substantially free of acompound in the central pore of the cyclodextrin ring.
 42. A chipcomprising a shaped polyolefin resin particulate with a major dimensionof less than about 10 millimeters and a weight of about 15 to about 50milligrams, the chip comprising the composition of claim
 1. 43. Acontainer comprising an enclosed volume surrounded by a polyolefin web,the web comprising the composition of claim
 1. 44. The container ofclaim 43 wherein the web comprises a laminate comprising a paperboardlayer and a bonded polyolefin layer.
 45. The container of claim 44wherein the web is filled with a liquid food.
 46. The container of claim45 wherein the web has a capacity of about 100 mL to 3 liters and theliquid food comprises a citrus juice.
 47. A film comprising thecomposition of claim
 1. 48. The film of claim 47 wherein the filmcomprises a laminate comprising a paperboard layer and a polyolefinlayer.